A kind of Synergistic mite killing composition containing flufenzine
Technical field
The present invention relates to a kind of insecticide acaricide composition, one kind is concretely related to containing flufenzine and substitution -1 of N- tri-,
The insecticide acaricide composition of 2,3- thiadiazoles -5- formamidine compounds, belongs to field of pesticide preparation.
Background technology
Mite class belongs to Arthropoda, and Arachnoidea, Acarina is individual smaller.All ranks are there may be in a colony
The mite of section, including ovum, deutonymph, young mite and into mite.It is mostly intensive to infest fruit tree, vegetables, cotton, peanut and other crops and view and admire plant
The vacuum side of blade of thing, and its breeding is rapid, high these of selfing degree all determine the more difficult preventing and treating of mite class.On the other hand, Nong Minyou
The continuous single acaricide good using miticidal effect of custom, as a result causes acarid that resistance is produced within many time and profit is lost
With value.Therefore, using the different mechanisms of action, different types of acaricide be solve evil mite be also easy to produce resistance effective way it
One.
Flufenzine is the tetrazine class acaricide developed in early 1990s by Hungarian Chinion companies,
It is the derivative of famous acaricide clofentezine (Closfentezine), but effect is typically four times of clofentezine.Flufenzine is former
Medicine crude product outward appearance is aubergine crystal, is white solid, structural formula Chinese 3- (2- fluorophenyls) -6- (2,6- bis- after purification
Fluorophenyl) -1,2,4,5- tetrazines, chemical formula C14H7ClF2N4, CAS accession number 162320-67-4, English abbreviation
Flufenzine, Chinese another name fluorine mite.187-189 °C of flufenzine sterling fusing point, is insoluble in water, is relatively soluble in acetone etc. organic molten
Agent.Because lipids is the main energy sources of mite ovum, flufenzine mechanism of action is destruction mite or mite ovum lipides
Use, so as to cause toxic action of the flufenzine to mite class.Flufenzine is at low concentrations(Active compound content is less than 25mg/kg)There is suppression
Evil mite processed casts off a skin, suppresses the effect that evil mite is laid eggs;In slightly higher concentration(Active compound content is higher than 37mg/kg)Just have and tag well
Property, while having good absorbability.Flufenzine is active to the mite ovum of tetranychid and young mite, harmless to beneficial insect, to predatory mite
Have no adverse effect.Its (LD50 is 979 mg/kg) low to mammalian toxicity, lasting period short (DT50 in the environment
For 30~44 d).Its mechanism of action is to suppress the growth of mite ovum and chrysalis phase mite, but is not yet proved.Flufenzine is to mandarin orange
The evil mites such as citrus red mite, Xiu Pi lices, yellow tea mite, Tetranychus cinnabarinus and Tetranychus urticae have fine preventive effect, can be used for citrus, grape etc.
The mite evil of the solanaceous crops such as fruit tree and eggplant, capsicum, tomato is administered.Additionally, flufenzine is to pear sucker, oystershell scale and leafhopper
The insects such as class have it is simultaneous well control effect, therefore have been generally acknowledged that mite killing spectrum is wide, strong adaptability.Ovicidal effect is especially excellent, while
Also there is good action of contace poison to children mite.Although flufenzine can not quickly kill female into mite, have very into mite to female
Good sterilisation-effect.It is female touch medicine into mite after the ovum that is produced have and 96% can not hatch, die from late embryogenesis, therefore have been generally acknowledged that fluorine mite
The characteristics of piperazine has eggs and young are both killed.The flufenzine drug effect lasting period is long, and citrus red mite (crm) is controlled with 6000 times of dilution liquid energies in production
Harm was up to 40~50 days.European Union is that agricultural chemicals controls most stringent of region, but the European Union in today uses the maximum amount of acaricide
Compound is exactly flufenzine, therefore can also reflect the flufenzine spy such as have low toxicity, low-residual, security good in terms of this
Point.
The synthetic method of flufenzine is relatively fewer, mainly there is two kinds of synthetic routes.Route one:It is with 2- chlorobenzoic acids first
Predominant starting material, through over-churning, the ammonolysis reaction of ester obtains 2- chlorobenzene formacyl hydrazines;Or 2- chlorobenzoic acids are main starting
Raw material, by with thionyl chloride into acyl chlorides, acyl chlorides again with hydration hydrazine reaction obtain 2- chlorobenzene formacyl hydrazines.2- chlorobenzene formacyl hydrazines
With 2,6- difluoro benzoyl chlorides effect generation N-2- chlorobenzene formacyls-N'-2,6- difluoro benzoyl hydrazine, then through superchlorination,
Cyclization, dehydrogenation reaction and product flufenzine is obtained.Route two:With 2,6- difluorobenzaldehydes and 2- chlorobenzaldehydes for initiation material,
Flufenzine has been obtained by condensation, chlorination, cyclization and dehydrogenation.
Although flufenzine has the distinctive advantages of numerous tools, in use it remain to be noted that:Can not with it is strong
Basic pesticides are used with;Can not be mixed with copper agent;In view of resistance management, flufenzine is most in the access times of a Growing season
No more than 4 times;The main effect model of flufenzine is to tag and stomach toxicity, medium absorbability, therefore spray wants complete stool even spraying,
Particularly blade back;Quite big when mite quantity is caused harm into, the middle and later periods for example caused harm in citrus red mite (crm), flufenzine individually makes
It is poor with effect quickly to kill into mite, it is necessary to be used in mixed way with other acaricides such as AVM etc., can control for a long time again
The recovery of evil mite population number processed.
Chinese patent(Application number CN2015100098343, January 9 2015 date of application, denomination of invention:Containing three nitrogen
1,2,3- thiadiazoles -5- formamidines the compound of heterocycle and synthesis)In report the artificial Xihua Univ of patent application(Inventor
Wang Hui towns, Liu Ping, Yang Wei are clear etc.)Formula for TDCA the polysubstituted -1,2,3- thiadiazoles -5- formamidines compounds of N- and its conjunction
Into method(Formula 1).Chinese patent(Application number CN2015100237806, January 19 2015 date of application)In report patent
Apply for artificial Xihua Univ(Inventor Liu Ping, Yang Wei are clear etc.)Mutual-through type is the polysubstituted -1,2,3- thiadiazoles -5- of N- of TDCA
The novel synthesis of formamidine compound are reported that the new method, using being first cyclized, finally goes up first to the synthesis of target product
The method of base, obtains fine experiment effect.Chinese patent(Application number CN2015103042053, June 9 2015 date of application
Day, denomination of invention:Cyclization method synthesizes polynitrogen heterocycle thiadiazoles -5- formamidine compounds)In report the artificial Xihua of patent application
University(Inventor Yang Wei is clear, Liu Ping etc.)Mutual-through type is the polysubstituted -1,2,3- thiadiazoles -5- formamidine compounds of N- of TDCA
Novel synthesis reported, the new method to the synthesis of target product using first going up methyl, the method being finally cyclized, this is new
Synthetic method high income, catalyst are easily prepared, catalyst is cheap, phosphorus-containing wastewater is few, to more environment-friendly.Chinese patent
(Patent No. ZL201510277765.4, May 28 2015 date of application, 2016 Granted publication dates August 31 days, invention
Title:1,2,3- thiadiazoles -5- formamidines poly-heterocyclic compounds are used as acaricidal purposes)In to report patent application artificially western
Hua Da(Inventor Yang Wei is clear, Liu Ping, Zhang Yuanyuan etc.)Formula for TDCA the polysubstituted -1,2,3- thiadiazoles -5- first of N-
Amidine compound as acaricidal purposes, particularly for the evil of fruit tree, vegetables, cotton, peanut and other crops and ornamental plant
Acarid control.But formula is the murder by poisoning power of the polysubstituted -1,2,3- thiadiazoles -5- formamidines compounds of N- to part adult of TDCA
It is not powerful enough, it is necessary to kill adult activity acaricide high(Such as AVM, flufenzine)Interworking is carried out to use.Many institute's weeks
Know, Insecticidal and acaricidal agent all easy insect during long-term use develops immunity to drugs, week is used for one new varieties of extension
Phase, interworking is carried out using being a kind of conventional strategy with other excellent insecticidal acaricide kinds.
The content of the invention
The main object of the present invention is directed to above deficiency, by the acaricidal rational mixture of the different mechanisms of action, there is provided
One kind has synergistic effect, and miticidal effect is good, safety, while can reduce the miticide composition of use cost again.
Chinese patent(Patent No. ZL201510277765.4, May 28 2015 date of application, Granted publication date
On August 31st, 2016, denomination of invention:1,2,3- thiadiazoles -5- formamidines poly-heterocyclic compounds are used as acaricidal purposes)Middle report
Road formula is the N- polysubstituted -1,2,3- thiadiazoles -5- formamidine compounds of TDCA(Formula 1)It is special as acaricidal purposes
It is not the control of pest mite for fruit tree, vegetables, cotton, peanut and other crops and ornamental plant.In formula in the compound of TDCA
TDCA-6~TDCA-12(The detailed titles of TDCA-6~TDCA-12 and structural formula are with reference to association patent, Chinese Patent Application No.
CN2015100098343)With preferable acaricidal activity, the factors such as mite killing broad spectrum activity, toxicity, production cost are considered,
TDCA-6(Formula 2)It is comparatively speaking more preferable acaricide in numerous compounds.Therefore, in following narrations of the invention, mainly with
It is the polysubstituted -1,2,3- thiadiazoles -5- formamidine compounds of the N- of TDCA that TDCA-6 represents formula.
What the object of the invention was realized in that:
Miticide composition of the present invention (the 5- tert-butyl group -1,3,4- thiadiazoles -2- bases)-N'- (2,6- dichloro pyrroles with Chinese as N-
Pyridine -4- bases)-N, [English name is N- (5-tert-butyl-1,3,4- to 4- dimethyl -1,2,3- thiadiazoles -5- carbonamidines
thiadiazol-2-yl)-N'- (2, 6-dichloropyridin-4-yl)-N,4-dimethyl-1,2,3-
thiadiazole-5-carboxam-idine(Hereinafter referred to as TDCA-6 in the present invention)], structural formula is as shown in formula 2
Compound and flufenzine be active ingredient, with agricultural chemicals in acceptable auxiliary element collectively constitute.
The permission part by weight of TDCA-6 and flufenzine is 60 in miticide composition of the present invention:1 to 1:80, it is preferably in a proportion of
10:1 to 1:40.
Miticide composition compound of the present invention has acaricidal purposes, particularly for fruit tree, vegetables, cotton, peanut
Deng crop and the control of pest mite of ornamental plant.The present composition is applied on crop and/or ornamental plant and is harmful to acarid life
Region long, can effectively prevent and treat evil mite.Present composition time of application can be in each growth phase in acarid, including
Ovum, deutonymph, young mite and into mite.Some representatives for the evil mite that can be prevented and treated for the present composition being mentioned below, enumerate and do not limit
Evil mite on some following crops and/or ornamental plant.
As the mite class for preventing and kill off as the present composition object, can enumerate:Belong to the mite of Ying Pi sections:Japanese blood mite,
Haemaphysalis longicornis, boophilus microplus, dermacentor reticulatus, dermacentor taiwanensis, haemaphysalis flava, ixodes persulcatus etc..Belong to the mite of Eriophyidae:Tea point leaf
Section tick, tealeaves goitre mite, apple rust mite, grape leaf rust mite, tulip aceria, matrimony vine burrknot tick, pseudo- pears rust tick, Pi Shi skin goitre mites
Deng.Belong to the mite of Tyroglyphidae:Hesperidium mite, ellipse dispersion, Acarus siro, the wild fat mite in river, Rhizoylyphus echinopus etc..Belong to Tarsonemidae
Mite:Webster tarsonemid, Polyphagotarsonemus latus Banks, primrose herbivore mite, double leaf tarsonemid.Belong to the mite of Eupodidae:Wheat leaf pawl mite,
Chinese cabbage mite.Belong to the mite of Tetranychidae:It is panonychus citri, panonychus ulmi, mulberry Panonychus citri, Tetranychus urticae, Tetranychus cinnabarinus, purplish red short
Must mite, priet mite, Liu Shi short hairs mite, Asia beginning tetranychid, knee beginning tetranychid, northern beginning tetranychid, Lee's beginning tetranychid, Eotetranychus smithi
Deng.
Although the present composition shows outstanding preventing and treating activity to the acarid of various mite sections, to useful crop, such as
Fruit tree, vegetables, cotton, peanut and other crops and/or ornamental plant only have the infringement of small degree or do not damage completely, take
Certainly in the present composition general structure concrete structure of each compound, amount of application, using useful crop object.Here it is this
Invention compound can be applied to the basic reason of control of pest mite on crop and/or ornamental plant.
Acceptable auxiliary element in described agricultural chemicals, including used in agricultural chemicals at present, unfavorable shadow will not be produced
Loud all kinds of common solvents and/or inert filler and/or surfactant and/or preservative and/or antifreezing agent and/or agglomeration resistance
Agent and/or defoamer and/or the corresponding adding ingredient such as cosolvent and/or stabilizer and/or thickener, it is possible to according to being produced
Dosage form do corresponding selection or adjust.
Agrochemical formulations generally comprise the miticide composition of the present invention of 0.1-99 weight %, particularly 2-90 weight %.
Wettable powder(WP)Middle miticide composition concentration is, such as 10-90 weight %, and the remainder in 100 weight % is by routinely making
Agent auxiliary element is constituted.In suspending agent(SC)Middle miticide composition concentration is, such as 1-90 weight %, preferably 5-75 weight %, 100
Remainder in weight % is made up of conventional formulation auxiliary element.In suspension emulsion(SE)Middle miticide composition concentration is, such as 1-
90 weight %, preferably 5-75 weight %, the remainder in 100 weight % are made up of conventional formulation auxiliary element.In water dispersant
(WDG)Middle miticide composition concentration is, such as 1-95 weight %, preferably 10-70 weight %, and the remainder in 100 weight % is by normal
Regulation agent auxiliary element is constituted.The preparation of other powder types includes 1-40 weight % reactive compounds, and preferably 5-20 weight % lives
Property compound, the remainder in 100 weight % is made up of conventional formulation auxiliary element.
Miticide composition of the present invention, using needing or applying Huan Jing ∕ conditions, is given birth to according to different by current conventional pesticide
Product mode, by TDCA-6 in the miticide composition and flufenzine active ingredient and corresponding auxiliary element for raw material is sufficiently mixed,
Prepare the available corresponding formulation as multi-form.Possible formulation includes:Wettable powder, water dispersant, suspension
Agent, aqueous emulsion, suspension emulsion, microcapsule formulations etc..Such as several typical common dosage forms and prepare can be with:
Microcapsule formulations(CJ)Refer to and form " core-shell structure copolymer " structure small container using natural or synthesis macromolecular material, by agricultural chemicals
Cladding wherein, and is suspended in the formulations of pesticide in water.Micro-capsule suspension outward appearance is a thick working fluid, with aqueous emulsion
And aqueous suspension agent is similar.Micro- sem observation is used, its profile of microcapsules is spherical in shape, rugby shape, grain or other shapes.Microcapsules
Diameter is general at 3-30 microns.Observed with 400 power microscopes and be about as much as small rice grain and mung bean grain size.Due to microcapsules agriculture
Medical instrument has that the lasting period is long, toxicity is low, safe ready the features such as, just as pesticides new formulation a developing direction.Microcapsules
Customary preparation methods have complex coacervation, Simple coacervation, interfacial polymerization, situ aggregation method, orifice-coagulating bath method etc..It is several recently
There are some novel processing steps, such as molecular inclusion, microchannel emulsification method, supercritical fluid quick expansion method, ferment again in year
Female microcapsule method, self-assembled multilayer film method.Microcapsules often have sodium alginate, shitosan, gelatin, porous-starch etc. with wall material.
Complex coacervation is most popular method in above-mentioned microcapsule preparation method.Complex coacervation preparation principle is to carry opposite charges with two kinds
Material make embedded object, core disperses wherein, to change change pH values, temperature or solution concentration, due to the effect between electric charge, makes two kinds
Wall material solubility declines and is condensed into microcapsules precipitation.A kind of positively charged colloidal solution and another negatively charged colloid
Solution is mixed, and is separated because the interaction between xenogenesis electric charge forms compound polyelectrolyte, is deposited on capsule-core week
Enclose and obtain microcapsules.Complex coacervation is often capsule material with gelatin, Arabic gum.Gelatin is protein, in aqueous, strand
Upper containing-NH2 and-COOH and its accordingly dissociation group-NH3+ and-COO-, but containing-NH3+ and-COO- ions how much, be situated between
The influence of matter pH value.Gelatin solution is in pH 4.0 or so, and its positive charge is most.Arabic gum is polysaccharide, in aqueous,
Containing-COOH and-COO- on strand, with negative electrical charge.Therefore in the aqueous solution that gelatin mixes with Arabic gum, pH is adjusted
When about 4.0, gelatin and Arabic gum neutralize to form compound on the contrary because of charged phase, the reduction of its solubility, are condensed from system
Encystation is separated out.Curing agent formaldehyde is added, formaldehyde produces amine aldehyde condensation reaction with gelatin, and gelatin molecule is cross-linked into network structure,
The shape of micro-capsule is kept, as irreversible micro-capsule;Plus 2% NaOH regulations medium pH 8 ~ 9, be conducive to amine aldehyde condensation reaction to enter
Row is complete.
Water dispersant(WDG)Can in water fater disintegration, and can be uniformly dispersed in higher suspension dispersion is formed in water
A kind of granular preparation.The present composition and auxiliary element one can be reinstated into air-flow during preparation to smash or ultra-fine grinding, system
Into wettable powder, this is dry method;By the present composition, auxiliary agent, adjuvant etc., with water as medium, ground in sand mill,
Suspending agent is made, then re-dry granulation, this is wet method.
Wettable powder(WP), i.e., solid powder preparation that can be dispersed in water.During preparation, can be according to conventional side
Formula, is firstly added the composition of TDCA-6 of the present invention and flufenzine, is subsequently adding diatomite, potter's clay, precipitated calcium carbonate, white carbon
Etc. conventional diluent or inert substance, other conventional auxiliary elements, such as alkylnaphthalene sulfonate, alkylbenzenesulfonate, fat are added
Fat alcohol sulfate, alkyl bromination ammonium, alkyl ammomium chloride, quaternary alkylphosphonium salts, alkyl polyoxyethylene base ether sulfate, lignosulfonates,
One or several in lignin, carboxymethylcellulose calcium, sodium carboxymethylcellulose, azone, thiophene ketone, and conventional stabilizer,
The complementary auxiliary component such as foam inhibitor, anticaking agent.
Suspension emulsion(SE)That is a kind of hybrid dispersions of the insoluble agricultural chemicals of water in water, active ingredient therein is in suspension
State, other active ingredients are in emulsion state.Can be by the present composition and corresponding emulsion, moistening point when being prepared during preparation
The auxiliary elements such as powder, thickener, stabilizer, antifreezing agent, pH adjusting agent, defoamer, conventionally, through wet method Ultramicro-powder
It is broken to be mixed to prepare.Wherein emulsifying agent is APES class(Agriculture breast 100#), alkylbenzenesulfonate(Agriculture breast 500#), benzene
Ethyl phenol polyethenoxy ether class(Agriculture breast 600#), alkyl phenol or aralkyl phenol polyethenoxy ether formaldehyde condensation species(Nongru-700 #)
One or several in.Wherein Ricinate is lignosulfonates, lignin, phosphate polyethers, carboxymethyl fibre
Dimension element, sodium carboxymethylcellulose, crown ether, alkylnaphthalene sulfonate, alkylbenzenesulfonate, aliphatic alcohol sulfate, alkyl ammonium halide, season
One or several in phosphonium salt, alkyl polyoxyethylene base ether sulfate, azone, thiophene ketone;Thickener and stabilizer are polyethylene
One or several in alcohol, condensed phosphate, xanthan gum, Magnesiumaluminumsilicate etc.;Antifreezing agent be sodium chloride, urea, ammonium sulfate,
One or several in ethylene glycol, glycerine etc.;PH adjusting agent be potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate,
One or several in potassium carbonate etc..Conventional organosilicon is used as defoamer and foam inhibitor.
Suspending agent(SC)That is agricultural chemicals suspension agent(SC), be water insoluble solids agricultural chemicals or mix liquid pesticidal in water or oil
Dispersion.During preparation, with water or oil as decentralized medium, by TDCA-6 of the present invention and flufenzine composition and auxiliary element
(Such as thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoamer)Through soybean dietary fiber(Grinding)System
.Wherein Ricinate is phosphate polyethers, alkylnaphthalene sulfonate, alkylbenzenesulfonate, aliphatic alcohol sulfate, alkyl bromide
Change ammonium, alkyl ammomium chloride, crown ether, quaternary alkylphosphonium salts, alkyl polyoxyethylene base ether sulfate, lignosulfonates, lignin, carboxymethyl
One or several in cellulose, sodium carboxymethylcellulose, azone, thiophene ketone;Thickener and stabilizer are polyvinyl alcohol, condensation
One or several in phosphate, xanthan gum, Magnesiumaluminumsilicate etc.;Antifreezing agent be sodium chloride, urea, ammonium sulfate, ethylene glycol,
One or several in glycerine etc.;PH adjusting agent is potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, potassium carbonate etc.
In one or several.Conventional organosilicon is used as defoamer and foam inhibitor.
It should be noted that specific formulation mentioned above is the representative formulation that present composition thing can be prepared, enumerate
It is not limited to these above-mentioned formulations.
To be administered, if by appropriate formulation, diluted in a usual manner, for example for wettable powder, water dispersant,
Suspending agent, aqueous emulsion, suspension emulsion dilute with water.Pulvis, granule, microcapsule formulations etc. generally no longer use other inert materials using preceding
Matter dilutes.
The amount of application of the compounds of this invention changes according to external condition, and the external condition especially prevents and treats acarid pair
As, temperature, humidity, preparation formulation.It can change in relative broad range, such as 0.1-500g/667m2 or more chemical combination of the present invention
Thing, preferably 1-50g/667m2.
Concrete mode by the following examples is described in further detail to the above of the invention again.But should not
This scope for being interpreted as above-mentioned theme of the invention is only limitted to following example by this.Above-mentioned technological thought feelings of the invention are not being departed from
Under condition, according to various replacements or change that ordinary skill knowledge and customary means are made, all should be included in of the invention
In the range of.Each material proportion of composing is weight % in embodiment.
Specific embodiment:
(1), example of formulations
Embodiment 1:6% miticide composition TDCA-6 flufenzine microcapsule formulations(CJ)(6% refers to original ingredient ratio, similarly hereinafter)
Weigh respectively 30 grams of TDCA-6,30 grams of flufenzines, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 grams Ah
Draw primary glue, 10 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetums appropriate(Titer is by the drop in preparation process
Fixed operation determines usage amount, similarly hereinafter), 20% NaOH solution(Titer), distilled water complementary to 1000 grams, it is standby;
Preparation process(1)Poly-aspartate is prepared with gelatin mixed solution:After using distillation appropriate amount of water immersion swelling in gelatin, heating
Dissolving, is heated to 50 DEG C, adds poly-aspartate, and stirring adds appropriate distilled water, and 50 DEG C of insulations are standby.(2)Arabic peptization
The preparation of liquid:Appropriate distilled water is added in reaction unit, Arabic gum powder is added, 80 DEG C or so are heated to, being gently mixed makes
Dissolving, 80 DEG C of insulations are standby.(3)The preparation of TDCA-6 and flufenzine active ingredient emulsion:By TDCA-6, flufenzine, tween-
60th, polyethylene glycol, the gumwater of above-mentioned preparation, are placed in tissue mashing machine, emulsify 30 seconds, obtain final product emulsion.(4)It is mixed
Close:Under the conditions of 50~55 DEG C, above-mentioned poly-aspartate and gelatin mixed solution are added, being gently mixed makes to be well mixed.(5)It is micro-
The preparation of capsule:In the case where being stirred continuously, to 10% acetum is added dropwise in foregoing mixed liquor, pH to 3.8~4.0 is adjusted;(6)Micro-capsule
Solidification:In the case where being stirred continuously, during about 30 DEG C of distilled water added into micro-capsule liquid, micro-capsule liquid will be contained and taken from 50~55 DEG C of water-baths
Under, it is stirred continuously, natural cooling, when temperature drops to 32~35 DEG C, ice cube is added, it is less than 10 DEG C to continue to stir to temperature,
Add 20% formalin, continue to stir 15~25min, then its pH 8~9 is adjusted with 20%NaOH solution, continue to stir 20~
30min, to separating out, standing treats that micro-capsule is settled for observation.(7)The filtering and drying of micro-capsule:Treat that micro-capsule sedimentation is complete, cross and filter
Fall supernatant, micro-capsule distillation is washed to formaldehydeless taste, centrifugation, drying.
Embodiment 2:6% miticide composition TDCA-6 flufenzine microcapsule formulations(CJ)
Weigh respectively 40 grams of TDCA-6,20 grams of flufenzines, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 grams Ah
Draw primary glue, 20 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetums appropriate(Titer), 20% NaOH solution(Titration
Amount), distilled water complementary to 1000 grams, it is standby;
Preparation process is completely same as Example 1.
Embodiment 3:6% miticide composition TDCA-6 flufenzine microcapsule formulations(CJ)
Weigh respectively 20 grams of TDCA-6,40 grams of flufenzines, 30 grams of gelatin, 20 grams of poly-aspartates, 10 grams of Tween-60s, 50 grams Ah
Draw primary glue, 8 grams of polyethylene glycol, 50 gram of 20% formalin, 10% acetums appropriate(Titer), 20% NaOH solution(Titration
Amount), distilled water complementary to 1000 grams, it is standby;
Preparation process is completely same as Example 1.
Embodiment 4:10% miticide composition TDCA-6 flufenzine microcapsule formulations(CJ)
Weigh respectively 50 grams of TDCA-6,50 grams of flufenzines, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s, 60 grams Ah
Draw primary glue, 30 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetums appropriate(Titer), 20% NaOH solution(Drop
It is quantitative), distilled water complementary to 1000 grams, it is standby;
Preparation process is similar to Example 1.
Embodiment 5:10% miticide composition TDCA-6 flufenzine microcapsule formulations(CJ)
Weigh respectively 33 grams of TDCA-6,67 grams of flufenzines, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s, 60 grams Ah
Draw primary glue, 25 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetums appropriate(Titer), 20% NaOH solution(Drop
It is quantitative), distilled water complementary to 1000 grams, it is standby;
Preparation process is similar to Example 1.
Embodiment 6:10% miticide composition TDCA-6 flufenzine microcapsule formulations(CJ)
Weigh respectively 67 grams of TDCA-6,33 grams of flufenzines, 40 grams of gelatin, 30 grams of poly-aspartates, 20 grams of Tween-60s, 60 grams Ah
Draw primary glue, 50 grams of polyethylene glycol, 100 gram of 20% formalin, 10% acetums appropriate(Titer), 20% NaOH solution(Drop
It is quantitative), distilled water complementary to 1000 grams, it is standby;
Preparation process is similar to Example 1.
Embodiment 7:50% miticide composition TDCA-6TDCA-13 flufenzine water dispersible granules(WDG)
250 grams of TDCA-6,50 grams of TDCA-13,200 grams of flufenzines, 50 grams of lignin, 50 grams of acrylic acid minor matters polymerizations are weighed respectively
Thing, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 8:30% miticide composition TDCA-6TDCA-10TDCA-13 flufenzine water dispersible granules
(WDG)
Weigh respectively 120 grams of TDCA-6,80 grams of TDCA-13,50 grams of TDCA-10,50 grams of flufenzines, 50 grams of lignin, 50 gram third
Olefin(e) acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 9:50% miticide composition TDCA-6TDCA-10TDCA-13 flufenzine water dispersible granules
(WDG)
Weigh respectively 240 grams of TDCA-6,50 grams of TDCA-13,50 grams of TDCA-10,160 grams of flufenzines, 50 grams of lignin, 50 gram third
Olefin(e) acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 10:60% miticide composition TDCA-6TDCA-10TDCA-13 flufenzine water dispersible granules
(WDG)
Weigh respectively 120 grams of TDCA-6,40 grams of TDCA-13,40 grams of TDCA-10,400 grams of flufenzines, 60 grams of lignin, 40 gram third
Olefin(e) acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 11:60% miticide composition TDCA-6TDCA-10TDCA-13 flufenzine water dispersible granules
(WDG)
Weigh respectively 100 grams of TDCA-6,100 grams of TDCA-13,100 grams of TDCA-10,300 grams of flufenzines, 50 grams of lignin, 30 grams
Acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 12:60% miticide composition TDCA-6TDCA-10TDCA-13 flufenzine water dispersible granules
(WDG)
Weigh respectively 150 grams of TDCA-6,150 grams of TDCA-13,150 grams of TDCA-10,150 grams of flufenzines, 60 grams of lignin, 40 grams
Acrylic acid minor matters polymer, 40 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 13:30% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)
Weigh respectively 200 grams of TDCA-6,100 grams of flufenzines, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 30 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 14:40% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)
Weigh respectively 220 grams of TDCA-6,180 grams of flufenzines, 60 grams of lignin, 50 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 60 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 15:30% miticide composition TDCA-13 flufenzine water dispersible granules(WDG)
Weigh respectively 200 grams of TDCA-13,100 grams of flufenzines, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 40 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 16:40% miticide composition TDCA-6 flufenzine wettable powders(WP)
Weigh respectively 360.0 grams of TDCA-6,40.0 grams of flufenzines, 30 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses,
30 grams of Magnesiumaluminumsilicates, 20 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 17:30% miticide composition TDCA-6 flufenzine wettable powders(WP)
200 grams of TDCA-6,100 grams of flufenzines, 30 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 30 are weighed respectively
Gram Magnesiumaluminumsilicate, 20 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 18:20% miticide composition TDCA-6 flufenzine wettable powders(WP)
100 grams of TDCA-6,100 grams of flufenzines, 35 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 40 are weighed respectively
Gram Magnesiumaluminumsilicate, 20 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 19:30% miticide composition TDCA-6 flufenzine wettable powders(WP)
100 grams of TDCA-6,200 grams of flufenzines, 30 grams of lignosulfonates calcium, 30 grams of sodium carboxymethylcelluloses, 30 are weighed respectively
Gram Magnesiumaluminumsilicate, 20 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 20:50% miticide composition TDCA-6 flufenzine wettable powders(WP)
100 grams of TDCA-6,400 grams of flufenzines, 40 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 40 are weighed respectively
Gram Magnesiumaluminumsilicate, 30 grams of neopelexes, 20 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 21:20% reactive compound(TDCA-6)Water dispersible granules(WDG)
200 grams of TDCA-6,70 grams of lignin, 60 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 80 are weighed respectively
Gram polyethylene glycol, bentonite complementary are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 22:20% flufenzine water dispersible granules(WDG)
200 grams of flufenzines, 70 grams of lignin, 60 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 80 are weighed respectively
Gram polyethylene glycol, bentonite complementary are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 23:35% flufenzine suspending agent(SC)
350 grams of flufenzines, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 30 grams of Magnesiumaluminumsilicates, 40 are weighed respectively
Gram neopelex, 60 grams of polyethylene glycol, water complementaries are standby to 1000 grams;
During each material sequentially added into reactor, just dispersion is carried out using high-speed shearing machine, be then ground in sand mill
Effect grain diameter of components is at 2~5 μm.
Embodiment 24:60% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)
Weigh respectively 400 grams of TDCA-6,200 grams of flufenzines, 60 grams of lignin, 45 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 55 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 25:50% miticide composition TDCA-10 flufenzine water dispersible granules(WDG)
Weigh respectively 300 grams of TDCA-10,200 grams of flufenzines, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 55 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 26:50% miticide composition TDCA-9 flufenzine water dispersible granules(WDG)
Weigh respectively 300 grams of TDCA-9,200 grams of flufenzines, 60 grams of lignin, 40 grams of acrylic acid minor matters polymer, 40 gram 12
Sodium alkyl sulfonate, 55 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 27:50% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)
Weigh respectively 200 grams of TDCA-6,300 grams of flufenzines, 50 grams of lignin, 40 grams of acrylic acid minor matters polymer, 30 gram 12
Sodium alkyl sulfonate, 40 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 28:30% miticide composition TDCA-6TDCA-10 flufenzine water dispersible granules(WDG)
100 grams of TDCA-6,100 grams of TDCA-10,100 grams of flufenzines, 30 grams of lignin, 40 grams of acrylic acid minor matters are weighed respectively to gather
Compound, 30 grams of dodecyl sodium sulfates, 40 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 29:60% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)
Weigh respectively 571.4 grams of TDCA-6,28.6 grams of flufenzines, 60 grams of lignin, 50 grams of acrylic acid minor matters polymer, 35 gram ten
Dialkyl sulfonates, 25 grams of polyethylene glycol, bentonite complementaries are standby to 1000 grams;
During each material sequentially added into reactor, it is well mixed, is then ground in sand mill, add suitable quantity of water, granulation is dried
Obtain final product water dispersible granules.
Embodiment 30:30% flufenzine wettable powder(WP)
300 grams of flufenzines, 60 grams of lignosulfonates calcium, 60 grams of sodium carboxymethylcelluloses, 50 grams of Magnesiumaluminumsilicates, 30 are weighed respectively
Gram neopelex, 25 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 31:30% TDCA-6 wettable powders(WP)
300 grams of TDCA-6,35 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 32 grams of Magnesiumaluminumsilicates, 25 are weighed respectively
Gram neopelex, 25 grams of TBABs, kaolin complementaries are standby to 1000 grams;
Prepare:During each material sequentially added into reactor, stirring is sufficiently mixed it, is crushed to 5~20 μm.
Embodiment 32:10% flufenzine suspending agent(SC)
100 grams of flufenzines, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 80 grams of Magnesiumaluminumsilicates, 60 are weighed respectively
Gram neopelex, 50 grams of polyethylene glycol, water complementaries are standby to 1000 grams;
During each material sequentially added into reactor, just dispersion is carried out using high-speed shearing machine, be then ground in sand mill
Effect grain diameter of components is at 2~5 μm.
Embodiment 33:10% TDCA-6 suspending agents(SC)
100 grams of TDCA-6,50 grams of lignosulfonates calcium, 60 grams of sodium carboxymethylcelluloses, 85 grams of Magnesiumaluminumsilicates, 70 are weighed respectively
Gram neopelex, 60 grams of polyethylene glycol, water complementaries are standby to 1000 grams;
During each material sequentially added into reactor, just dispersion is carried out using high-speed shearing machine, be then ground in sand mill
Effect grain diameter of components is at 2~5 μm.
By following experiment it can be shown that two active ingredient TDCA-6 and flufenzine in above-mentioned miticide composition of the invention
Compounding can have obvious synergistic effect.
(2), biological Examples
Embodiment 34:TDCA-6 and flufenzine composite formula screening experiment
First, reagent agent(A represents flufenzine in following reagents;B represents TDCA-6)
A agent:30% flufenzine wettable powder(WP)(Prepared by the method for embodiment 30)
B agent:30% TDCA-6 wettable powders(WP)(Prepared by the method for embodiment 31)
AB1:Flufenzine TDCA-6(A:B=2:1)
AB2:Flufenzine TDCA-6(A:B=1:1)
AB3:Flufenzine TDCA-6(A:B=1:2)
AB4:Flufenzine TDCA-6(A:B=1:5)
AB5:Flufenzine TDCA-6(A:B=1:10)
AB6:Flufenzine TDCA-6(A:B=1:20)
AB7:Flufenzine TDCA-6(A:B=1:40)
AB8:Flufenzine TDCA-6(A:B=1:60)
2nd, for examination insect
For examination insect using the red spider adopted in the citrus trees of field, raised for 3 generations indoors as test worm.
3rd, experimental technique
Experiment uses dip slide method.Every kind of reagent tests 5 kinds of concentration(Every kind of specific concentration of reagent refers to table 1), each repeats to process
Three times, 120 are repeated every time, 72 hours microscopy results after medicine obtain the death rate for test worm, calculate LC50 and co-toxicity coefficient
(CTC).
4th, computational methods
The death rate of every kind of reagent is converted to correspondence niqueMin(y)It is ordinate, and with the right of the various concentrations of various reagents
Numerical value lgx is abscissa, using least square method, obtains virulence equation(y=a+blgx)Middle coefficient a, b.According to virulence equation,
As y=5.000(NiqueMin when i.e. the death rate is 50%), calculate the LC50 of the reagent.Calculated using the abundant equations of Sun Yun
The co-toxicity coefficient of confection(CTC)(Bibliography:Tan Genjia, wish Jianping etc., " fungicide bioassay computational methods and should
With ", Anhui agronomy circular, 1998,4(1), 27-28).The CTC values calculated using the abundant equations of Sun Yun, China is generally acknowledged that
CTC has synergistic effect more than 150(Wherein:CTC has notable synergistic effect more than 200), CTC is 50~150 for addition is made
With CTC is antagonism less than 50.
5th, result and analysis
TDCA-6 and flufenzine composition series proportioning mixture are to citrus red mite Toxicity Determination result, LC50 and common poison system
Number(CTC)It is shown in Table 1, table 2.
Laboratory experiment result shows, TDCA-6 and flufenzine composition series proportioning mixture do not show short of money to citrus red mite
Anti- effect, major part has certain synergistic effect(The CTC values of AB4~AB6 both greater than 150, show there is synergistic effect), AB4,
AB5 its CTC value is all higher than 200, shows there is notable synergistic effect.The co-toxicity coefficient of wherein AB4 mixtures is maximum(CTC=215), say
Bright its synergistic effect is maximum.
Table 1, TDCA-6 and flufenzine match mixture to citrus red mite Toxicity Determination result
The LC50 of table 2 and co-toxicity coefficient(CTC)
The death rate corresponding probit value when y represents composition series proportioning mixture various concentrations in table 2, x represents concentration(C)It is right
Numerical value lgC(That is x=lgC).
Embodiment 35:Flufenzine TDCA-6 composition for preventing and controlling citrus red mites field efficacy is tested
First, reagent agent
1st, 40% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)(It is prepared by the method according to embodiment 14);
2nd, 20% miticide composition TDCA-6 flufenzine wettable powders(WP)(It is prepared by the method according to embodiment 18);
3rd, 10% flufenzine suspending agent(SC)(It is prepared by the method according to embodiment 32);
4th, 10% TDCA-6 suspending agents(SC)(It is prepared by the method according to embodiment 33).
2nd, experimental subjects
1st, place is tested:Mianyang City Nong Ke areas of Sichuan Province live kwan-yin village Citrus Orchard;
2nd, crop is tested:Sweet orange;
3rd, controlling object:Citrus red mite.
3rd, experimental technique
1st, processing item:40% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)8000 times of dilution;20% kills
Acaricidal composition TDCA-6 flufenzine wettable powders(WP)4000 times of dilution;10% flufenzine suspending agent(SC)Dilution 2000
Times;10% TDCA-6 suspending agents(SC)2000 times of dilution.Blank:Using clear water.
2nd, cell is set:Each cell seeds, the age of tree, growing way and rich water quality management condition are basically identical.Each cell is fixed 3
Set, four repetitions, totally 24 cell;And cell is arranged according to random area.
3rd, spraying time and method:In citrus red mite peak of occurrence period(June 21)Dispenser is once.Using pressure manually
Contracting sprayer even spraying, to squirt blade as degree.
4th, control time and method:Before dispenser and 3 days after dispenser, respectively investigate once within 10 days, 20 days, 30 days.Method is
Each tree wins 30 leaves at random in four orientation, and 360 are won per cell, and mite quantity living on record blade calculates mite mouthful and subtracts
Move back rate and preventive effect.
4th, experimental result
40% miticide composition TDCA-6 flufenzine water dispersible granules(WDG)8000 times of dilution;20% miticide composition
TDCA-6 flufenzine wettable powders(WP)4000 times of dilution, is respectively 94.58% in 3 days after dispenser to citrus red mite preventive effect
With 95.71%;91.94% and 91.05% were respectively to citrus red mite preventive effect in 10 days after dispenser;After dispenser 20 days to the red spider of citrus
Spider preventive effect is respectively 83.27% and 84.36%;78.55% and 79.28% were respectively to citrus red mite preventive effect in 30 days after dispenser.It is right
According to the flufenzine suspending agent of medicament 10%(SC)2000 times of dilution, 3 days after dispenser, investigates preventive effects point in 10 days, 20 days, 30 days four times
Wei 92.04%, 89.01%, 81.41%, 71.80%.The TDCA-6 suspending agents of comparison medicament 10%(SC)2000 times of dilution, dispenser
Investigate preventive effects and be respectively 83.66%, 78.33%, 72.59%, 63.72% within 3 days afterwards, 10 days, 20 days, 30 days four times(Refer to table 3).Root
Observed according to field experiment, do not it is found that TDCA-6 flufenzines miticide composition produces poisoning phenomenon to experiment crop.
The TDCA-6 of table 3 and flufenzine series proportioning mixture are to citrus red mite field experiment result statistical form